Scientific American Supplement, No. 810, July 11, 1891Various
Science
Scientific American Supplement, No. 810, July 11, 1891
Various
Science -- Periodicals
Of the above two methods, that in which an ammonium oxalate solution
is used is the more delicate, although it cannot be employed
quantitatively, owing to the oxidation of the metal that takes place.
An addition of 1 grm. of ammonium oxalate to the suspected solution is
sufficient.
_Copper_.--0.00005 grm. of copper can be very readily detected by
electrolyzing an acid solution in the usual way. A spiral of platinum
wire is employed as the cathode, and the presence of the metal
confirmed for by dissolving it in a little nitric acid, diluting with
water and adding potassium ferrocyanide.
To detect these metals in cases of poisoning, the organic matter with
which they are associated must first be destroyed in the usual way by
means of hydrochloric acid and potassium chlorate, and the
precipitates obtained in the ordinary course of analysis, then
subjected, at suitable stages, to electrolysis. As the solutions thus
obtained will be still contaminated by some organic matter, it is
necessary to pass the current for a longer time than indicated above.
On the other hand, _urine_ can be tested directly for these poisons.
The presence of mercury or of copper may be detected by acidifying the
urine with 2-3 c.c. of nitric acid (conc.), and electrolyzing as
described. 0.0001 grm. of metal in 30 c.c. of urine can be detected
thus, or 1 part in 300,000 of urine.
Lead does not separate well as peroxide from urine, but if ammonium
oxalate be added, and the lead deposited as metal, the reaction is
quite as delicate as in aqueous solution, and 0.0001 grm. of lead can
be thus detected.
With antimony it is advisable to precipitate it first as sulphide, but
it can be detected directly, though not so satisfactorily, by
acidifying the urine with 2-3 c.c. of sulphuric acid (dil.), and
electrolyzing with a current of 1-5 to 2 c.c. In this case also it is
precipitated as metal upon the cathode (cp. Chittenden, Proceedings
Connecticut Acad. Science, Vol. 8).
In the presence of urine it is advisable to continue the passage of
the current for about twice the time required in the case of aqueous
solutions.
That an approximately quantitative result can be obtained under the
above conditions was shown in several cases in which deposition of
0.001 grm. of metal was confirmed with considerable accuracy, the
spiral or foil being weighed before and after the experiment.
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